Film forming polymer compositions for boosting spf in sunscreens

ABSTRACT

Film-forming compositions comprising a film forming polymer containing acid groups and a neutralizing agent; compositions and methods for increasing the SPF of a composition by neutralizing at least a portion of the acid groups of the film forming agent with the neutralizing agent.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a continuation application of U.S. application Ser.No. 13/398,930, filed Feb. 17, 2012, which is a continuation applicationof U.S. application Ser. No. 12/628,924, filed Dec. 1, 2009, whichclaims priority to U.S. Application Ser. No. 61/172,916, filed Apr. 27,2009, and to EP 09163327.1, filed Jun. 22, 2009, the contents of whichare each hereby incorporated by reference into this specification in itsentirety.

FIELD OF INVENTION

This invention relates generally to compositions applied topically tosurfaces, for example skin and hair, for protection against ultravioletradiation. The invention also relates to compositions and methods toimprove skin feel and sunscreening capacity of such compositions.

BACKGROUND OF THE INVENTION

Sunscreen compositions are typically categorized as either aqueous ornon-aqueous, i.e, anhydrous, compositions. Aqueous sunscreencompositions are typically creams formed as emulsions containing theactive UV absorbing compounds and additional ingredients such aswaterproofing agents, fragrances, emollients and other skin careingredients. Non-aqueous sunscreen compositions are those that aretypically solvent based compositions that can be formed as gels fortopical application or sprayed on, for example from an alcohol basedsolution of the ingredients.

Sprayable sunscreen compositions have become popular in recent years asa means for transporting and applying sunscreen. Film forming polymersare known to be added to non-aqueous sunscreen compositions to providewater resistance to these compositions after application to a surfacesuch as skin or hair. However, it has been determined that the additionof the film forming polymers beyond a certain amount can have adeleterious effect on the feel of the composition on the skin, inparticular providing a caking feeling. Neutralizing agents have beenused in connection with film forming agents contained in aqueoussunscreen emulsion formulations. See, e.g., WO 2004/071749 (ConneticsAustralia Pty. Ltd.) discussing limiting the amount of neutralizingagent added to aqueous formulations to preserve film forming properties.

In an effort to improve the skin feel of topically applied aqueousvolatile solvent-based sunscreen compositions that employ film formingpolymers as waterproofing agents, the inventors have discovered thatcertain neutralizing agents provide not only the desired improved skinfeel, but also provide an unexpected substantial boost in SPF values.Thus, compositions and methods employing such neutralizing agents toprovide for improved sunscreen protection would be useful. These andother objectives are provided by the invention described herein.

All patent and non-patent references cited herein are herebyincorporated in their entirety into this specification by referencethereto. Identification or discussion of any reference in this sectionor any part of this specification shall not be construed as an admissionthat such reference is available as prior art to the presentapplication.

SUMMARY OF THE INVENTION

The invention provides an aqueous volatile solvent-based compositioncomprising at least one UV absorbing active ingredient and at least onefilm forming polymer containing a plurality of acid groups, wherein thepolymer is present in an amount greater than about 1% by weight of thecomposition and wherein at least a portion of the acid groups have beenneutralized with a neutralizing agent.

The invention further provides a method for increasing the SPF for anaqueous volatile solvent-based composition comprising at least onesunscreen active agent and at least one film forming polymer, whereinthe film forming polymer comprises a plurality of acid groups, themethod comprising adding a cosmetically acceptable neutralizing agent tothe composition resulting in the formation of a composition containingat least one sunscreen active agent and a film forming agent wherein atleast a portion of the acid groups are neutralized by a cosmeticallyacceptable neutralizing agent, and wherein the film forming agent ispresent in an amount greater than 1% by weight of the final composition.

The invention also provides a method for increasing the SPF of anaqueous volatile solvent-based composition comprising at least onesunscreen active agent, which comprises adding to the composition a filmforming polymer containing a plurality of acid groups and a cosmeticallyacceptable neutralizing agent, resulting in the formation of acomposition containing said at least one sunscreen active agent and afilm forming agent wherein at least a portion of the acid groups areneutralized by said neutralizing agent, wherein the film forming polymeris present in an amount greater than 1% by weight of the finalcomposition.

The invention further provides a method for increasing the SPF of anaqueous volatile solvent-based composition comprising at least onesunscreen active agent, which comprises contacting a film formingpolymer containing a plurality of acid groups with a cosmeticallyacceptable neutralizing agent to form a neutralized film forming agentwherein at least a portion of the acid groups are neutralized by saidneutralizing agent, and adding to the composition comprising at leastone sunscreen active agent the neutralized film forming agent, resultingin the formation of a composition containing said at least one sunscreenactive agent and said neutralized film forming agent, wherein the filmforming agent is present in an amount greater than 1% by weight of thefinal composition.

The invention further provides a method for reducing the deleteriouseffects of UV radiation that contacts a surface which comprises applyingto the surface the compositions of the invention.

The invention also provides a method for preventing or reducing theoccurrence of erythema on a subject due to exposure to UV radiationwhich comprises applying the composition of the invention to the subjectprior to exposure to UV radiation.

The invention also provides a method for preventing or reducing theoccurrence of phototoxic or photoallergic reactions in a subject due toexposure to UV radiation which comprises applying the composition of theinvention to the subject prior to exposure to UV radiation.

DETAILED DESCRIPTION OF THE INVENTION

The invention provides an aqueous volatile solvent-based compositioncomprising at least one UV absorbing active ingredient and at least onefilm forming polymer containing a plurality of acid groups, wherein thepolymer is present in an amount greater than 1% by weight of thecomposition and wherein at least a portion of the acid groups have beenneutralized with a cosmetically acceptable neutralizing agent.

While many cosmetically acceptable neutralizing agents are available andwill function in this application, surprisingly amine-based neutralizingagents provide a synergistic boost in SPF levels. The amine-basedneutralizing agents of the invention can comprise a primary, secondary,or tertiary amine containing one or more hydrocarbon chains having atleast 3 carbon atoms. Thus, in one example embodiment, the neutralizingagent of the invention comprises one or more amines of the structure I:

wherein R₁ is H or a C₃-C₃₆, in another embodiment, C₃-C₂₄, and in stillanother embodiment, C₆-C₁₈ straight chain, branched or cyclic alkyl,alkenyl, alkynyl, aryl, aralkyl, aralkenyl, or aralkynyl group, R₂, R₃,are independently selected from H, CH₃, or a C₂ to about C₃₆ straightchain, branched or cyclic alkyl, alkenyl, alkynyl, aryl, aralkyl,aralkenyl, or aralkynyl group, provided that R₁, R₂, and R₃ are not allH. The alkyl, alkenyl, alkynyl, aryl, aralkyl, aralkenyl, and aralkynylgroup may optionally comprise one or more heteroatoms including S, N, O,and Si. In one embodiment of this invention, the one or more side chains(R₁, R₂ and R₃) will contain six or more carbon atoms (total of allchains). In another embodiment one chain will contain six or more carbonatoms.

In certain embodiments the amine-based neutralizing agents of theinvention will comprise one or more of the structures Ia-Id:

wherein R₄, R₅, R₆, and R₇, are independently selected from H, CH₃, or aC₂ to about C₃₆ straight chain, branched or cyclic alkyl, alkenyl,alkynyl, aryl, aralkyl, aralkenyl, or aralkynyl group. The alkyl,alkenyl, alkynyl, aryl, aralkyl, aralkenyl, and aralkynyl group mayoptionally comprise one or more heteroatoms including S, N, O, and Si.

Compounds of this type include the products known as JEFFAMINE®polyetheramines (available from Huntsman Chemical Co, The Woodlands,Tex.), including those having the following structures Ie through Ih:

wherein R₆ is H or CH₃;

wherein R₇ is H or C₂H₅.

In another embodiment, the amine-based neutralizing agent is selectedfrom one or more compounds of structures II and/or III:

wherein R₈, R₉, R₁₀, R₁₁, R₁₂ are independently H, CH₃, or a C₂ to aboutC₃₆ straight chain, branched or cyclic alkyl, alkenyl, alkynyl, aryl,aralkyl, aralkenyl, or aralkynyl group. The alkyl, alkenyl, alkynyl,aryl, aralkyl, aralkenyl, and aralkynyl group may optionally compriseone or more heteroatoms including S, N, O, and Si.

In another example embodiment, the neutralizing agent of the inventionmay also comprise amine groups contained within or pendant fromadditional molecules, such as a monomer unit within a larger polymer orpendant from a polymer backbone. Thus neutralizing agent may compriseprimary or secondary amines as pendant groups or monomer units whereinthe amines can be optionally substituted with C₂ to a C₃₆ straightchain, branched or cyclic alkyl, alkenyl, alkynyl, aryl, aralkyl,aralkenyl, or aralkynyl group. The alkyl, alkenyl, alkynyl, aryl,aralkyl, aralkenyl, and aralkynyl group may optionally comprise one ormore of S, N, O, or Si. The polymer backbone contemplated herein maycomprise, for example, a silicone polymer or acrylic acid polymer.

In certain example embodiments as shown structurally above, each of n,x, y, and z, are independently from 0 up to 100, up to 90, up to 80, upto 70, up to 60, up to 50, up to 40, up to 30, up to 20, or up to 10. Incertain example embodiments of the invention, R₁, R₂, R₃, and R₄ willindependently comprise moieties having up to 50 carbon atoms. In certainexample embodiments, R₁-R₁₂ will independently comprise moieties havingup to 40 carbon atoms. In certain example embodiments, R₁-R₁₂ willindependently comprise moieties having up to 30 carbon atoms. In certainexample embodiments, R₁-R₁₂ will independently comprise moieties havingup to 20 carbon atoms. Some non-limiting examples of amine neutralizingagents appropriate for this invention are alkyl amines, alkenyl amines,dialkyl amines, dialkenyl amines, dimethyl alkyl amines (alkyl beingstearyl, tallow, cocoyl, soy etc,), methyl dialkyl amines (alkyl beingstearyl, hexadecyl, tallow) and trialkyl amines, dimethyl alkenyl amines(alkenyl being soy, oleic, linoleic and linolenic), methyl dialkenylamines and trialkenyl amines and combinations thereof.

In the practice of the invention, the amine neutralizing agent acts toneutralize at least a portion of the acid groups, e.g., carboxylic,sulfonic, phosphoric or similar acid groups, on the film formingpolymer. Thus, the film forming polymer can be partially neutralized orfully neutralized by the neutralizing agent. In certain exampleembodiments between about 5% and about 100% the acid groups on the filmforming polymer will be neutralized. In other example embodiments up toabout 90%, up to about 80%, up to about 70%, up to about 60%, up toabout 50%, up to about 40%, up to about 30%, up to about 25%, up toabout 20%, up to about 15%, up to about 10% or up to about 5% of theacid groups on the film forming polymer will be neutralized.

In the practice of the invention, the amount of amine neutralizing agentto be added to obtain the desired percent neutralization of the polymerfilm forming agent can be determined based on the acidity of the polymerand the neutralization equivalent of the amine neutralizing agent. Forexample, the following equation can be used to determine the preciseamount of neutralizing agent:

${{Amount}\mspace{14mu} {of}\mspace{14mu} {Neutralizing}\mspace{14mu} {{Agent}(g)}} = \frac{W*A*N*E}{100,000}$

-   -   W=wt. of polymer film former in grams    -   A=acidity of polymer film former (meq/g)    -   N=% of desired neutralization    -   E=neutralization equivalent of amine (g/eq)

The acidity of particular film forming agents is readily available. Forexample the acidity of the film forming polymer DERMACRYL® 79 is 2.27meq/g. The neutralization equivalent (E) for various amine neutralizingagents is also readily available. Examples of some Armeen® and Ethomeen®amine neutralizing agents is shown in Table 1 below.

TABLE 1 Neutralization Product Name INCI Name Equivalent (g/eq) Armeen ®M2C Methyl Dicocamine 398 Armeen ® DMSVD Dimethyl Soyamine 306 Armeen ®DMCD Dimethyl Cocamine 240 Ethomeen ® SV12 PEG-2 Soyamine 357 Ethomeen ®C12 PEG-2 Cocamine 292 Ethomeen ® SV15 PEG-5 Soyamine 474 Ethomeen ® C15PEG-5 Cocamine 413 Ethomeen ® SV25 PEG-15 Soyamine 935 Ethomeen ® C25APEG-15 Cocamine 848

In the practice of the invention, the amine neutralizing agent may becombined with the film forming polymer to provide a partially or fullyneutralized polymer to be added later to the remainder of thecomposition. Alternatively, the amine neutralizing agent may be addedwith the film forming polymer as part of the composition, accomplishingthe partial or complete neutralization in situ.

In one example embodiment of the invention, the film forming polymercomprises at least 5% by weight of an acid-containing monomer. Inadditional example embodiments, the film forming polymer comprises atleast 5% by weight of an carboxylic acid-containing monomer.Non-limiting examples of these monomers are acrylic acid, crotonic acid,methacrylic acid, maleic acid, itaconic acid and combinations andmixtures thereof. Additional film forming polymers, either synthetic ornatural can be used with the acid containing polymers described above.Non-limiting examples of these additional film forming polymers are:from National Starch and Chemical Company, AMPHOMER® and AMPHOMER® LV-71polymers (octylacrylamide/acrylates/butylaminoethyl methacrylatecompolymer), AMPHOMER® HC polymer (acrylates/octylacrylamide copolymer)BALANCE® 0/55 and BALANCE® CR polymers (acrylates copolymer), BALANCE®47 polymer (octylacrylamide/butylaminoethyl methacrylate copolymer),RESYN® 28-2930 polymer (VA/crotonates/vinyl neodecanoate copolymer),RESYN® 28-1310 polymer (VA/Crotonates copolymer), FLEXAN® polymers(sodium polystyrene sulfonate), DynamX polymer (polyurethane-14 (and)AMP-Acrylates copolymer), RESYN® XP polymer (acrylates/octylacrylamidecopolymer), STRUCTURE® 2001 (acrylates/steareth-20 itaconate copolymer)and STRUCTURE® 3001 (acrylates/ceteth-20 itaconate copolymer); from ISP,OMNIREZ-2000® (PVM/MA half ethyl ester copolymer), GANEX P-904®(butylated PVP), GANEX V-216® (PVP/hexadecene copolymer) GANEX® V-220(PVP/eicosene copolymer), GANEX® WP-660 (tricontanyl PVP), GANTREZ® A425(butyl ester of PVM/MA copolymer), GANTREZ® AN-119 PVM/MA copolymer,GANTREZ® ES 225 (ethyl ester of PVM/MA copolymer), GANTREZ® ES425 (butylester of PVM/MA copolymer), GAFFIX® VC-713 (vinylcaprolactam/PVP/dimethylaminoethyl methacrylate copolymer), GAFQUAT® 755(polyquaternium-11), GAFQUAT HS-100® (polyquaternium-28) AQUAFLEX® XL-30(Polyimide-1), AQUAFLEX® SF-40 (PVP/Vinylcaprolactam/DMAPA AcrylatesCopolymer), AQUAFLEX® FX-64(Isobutylene/Ethylmaleimide/Hydroxyethylmaleimide Copolymer), ALLIANZ®LT-120 (Acrylates/C1-2 Succinates/Hydroxyacrylates Copolymer), STYLEZE®CC-10 (PVP/DMAPA Acrylates Copolymer), STYLEZE® 2000(VP/Acrylates/Lauryl Methacrylate Copolymer), STYLEZE® W-20(Polyquaternium-55), Copolymer Series(PVP/Dimethylaminoethylmethacrylate Copolymer), ADVANTAGE® S andADVANTAGE® LCA (VinylcaprolactamNP/Dimethylaminoethyl MethacrylateCopolymer), ADVANTAGE® PLUS (VA/Butyl Maleate/Isobornyl AcrylateCopolymer); from BASF, ULTRAHOLD STRONG (acrylic acid/ethylacrylate/t-butyl acrylamide), LUVIMER® 100P (t-butyl acrylate/ethylacrylate/methacrylic acid), LUVIMER® 36D (ethyl acrylate/t-butylacrylate/methacrylic acid), LUVIQUAT® HM-552 (polyquaternium-16),LUVIQUAT® HOLD (polyquaternium-16), LUVISKOL® K30 (PVP) LUVISKOL® K90(PVP), LUVISKOL® VA 64 (PVP/VA copolymer) LUVISKOL® VA73W (PVP/VAcopolymer), LUVISKOL® VA, LUVISET® PUR (Polyurethane-1), LUVISET® Clear(VP/MethacrylamideNinyl Imidazole Copolymer), LUVIFLEX® SOFT (AcrylatesCopolymer), ULTRAHOLD® 8 (Acrylates/Acrylamide Copolymer), LUVISKOL®Plus (Polyvinylcaprolactam), LUVIFLEX® Silk (PEG/PPG-25/25Dimethicone/Acrylates Copolymer); from Amerchol, AMERHOLD® DR-25(acrylic acid/methacrylic acidlacrylates/methacrylates); from Rohm&Haas,ACUDYNE® 258 (acrylic acid/methacrylicacid/acrylates/methacrylates/hydroxy ester acrylates; from Mitsubishiand distributed by Clariant, DIAFORMER® Z-301, DIAFORMER® Z-SM, andDIAFORMER® Z-400 (methacryloyl ethyl betaine/acrylates copolymer),ACUDYNE® 180 (Acrylates/Hydroxyesters Acrylates Copolymer), ACUDYNE® SCP(Ethylenecarboxyamide/AMPSA/Methacrylates Copolymer), and the ACCLTLYN®rheological modifiers; from ONDEO Nalco, FIXOMER® A-30 and FIXOMER® N-28(INCI names: methacrylic acid/sodium acrylamidomethyl propane sulfonatecopolymer); from Noveon, FIXATE® G-100 (AMP-Acrylates/Allyl MethacrylateCopolymer), FIXATE PLUS® (Polyacrylates-X), CARBOPOL® Ultrez 10(Carbomer), CARBOPOL® Ultrez 20 (Acrylates/C10-30 Alkyl AcrylatesCopolymer), AVALURE® AC series (Acrylates Copolymer), AVALURE® UR series(Polyurethane-2, Polyurethane-4, PPG-17/IPDI/DMPA Copolymer);polyethylene glycol; water-soluble acrylics; water-soluble polyesters;polyacrylamides; polyamines; polyquaternary amines; styrene maleicanhydride (SMA) resin; polyethylene amine; and other conventionalpolymer that is polar solvent soluble or that can be made solublethrough neutralization with the appropriate base.

Additional natural film forming polymers are native starch as usedherein, also starches derived from a plant obtained by standard breedingtechniques including crossbreeding, translocation, inversion,transformation or any other method of gene or chromosome engineering toinclude variations thereof. In addition, starch derived from a plantgrown from artificial mutations and variations of the above genericcomposition, which may be produced by known standard methods of mutationbreeding, are also suitable herein.

One skilled in the art would recognize that the film forming polymer maycomprise a blend of two of more polymers. In one example embodiment ofthe invention, a blend of polymers may be used, wherein at least one ofthe polymers contains a carboxylic acid monomer and the level ofcarboxylic acid monomer is no less than 5% of the total polymer (byweight dry basis of the total film forming polymer).

Sunscreen compositions according to the invention are prepared asaqueous volatile solvent-based compositions, meaning non-emulsioncompositions containing primarily volatile solvents and up to about 30%by weight water. Thus, the compositions comprise a single liquid phasethat may further comprise dispersed particulates. In certainembodiments, the compositions of the invention contain up to about 25%by weight water or up to about 20% by weight water. In additionalembodiments of the invention the compositions comprise between about 10%and about 30% by weight water, between about 10% and about 25% water orbetween about 10% and about 20% water. Example volatile solvents includeone or more of alcohols such as methanol, ethanol and isopropanol,volatile hydrocarbons such as isooctane, isododecane, and isohexadecane,aldehydes and volatile silicones also including volatile ketones such asacetone and methyl ethyl ketone. In an embodiment of this invention thevolatile solvent is chosen from the group consisting of ethanol,methanol, isopropanol and acetone. The sunscreen compositions of theinvention containing alcohol based solvent systems are characterized asnon-aqueous solutions. However, it may be desirable to have small amountof water in the composition, for example as a processing aid orco-solvent. In certain example embodiments, the water contents of thecompositions will be no greater than about 9% water so as to prevent theactive to phase separate or precipitate out of solution. Those ofordinary skill in the art will recognize that different actives havedifferent tolerance for water in solution and will adjust water contentaccordingly. Additionally, the solvent can include an oil such asmineral or vegetable oil. The oil may be the only solvent or may be usedin varying amounts as a co-solvent or as described herein as“emollients”.

For purposes of the present invention, a “sunscreen active agent” or“sunscreen active” shall include all of those materials, singly or incombination, that are regarded as acceptable for use as activesunscreening ingredients based on their ability to absorb UV radiation.Such compounds are generally described as being UV-A, UV-B, or UV-A/UV-Bactive agents. Approval by a regulatory agency is generally required forinclusion of active agents in formulations intended for human use. Thoseactive agents which have been or are currently approved for sunscreenuse in the United States include organic and inorganic substancesincluding, without limitation, para aminobenzoic acid, avobenzone,cinoxate, dioxybenzone, homosalate, menthyl anthranilate, octylsalicylate, oxybenzone, padimate O, phenylbenzimidazole sulfonic acid,sulisobenzone, trolamine salicylate, titanium dioxide, zinc oxide,diethanolamine methoxycinnamate, digalloy trioleate, ethyldihydroxypropyl PABA, glyceryl aminobenzoate, lawsone withdihydroxyacetone, red petrolatum. Examples of additional sunscreenactives that have not yet been approved in the US but are allowed informulations sold outside of the US include ethylhexyl triazone, dioctylbutamido triazone, benzylidene malonate polysiloxane, terephthalylidenedicamphor sulfonic acid, disodium phenyl dibenzimidazole tetrasulfonate,diethylamino hydroxybenzoyl hexyl benzoate, bis diethylaminohydroxybenzoyl benzoate, bis benzoxazoylphenyl ethylhexylimino triazine,drometrizole trisiloxane, methylene bis-benzotriazolyltetramethylbutylphenol, and bis-ethylhexyloxyphenolmethoxyphenyltriazine, 4-methylbenzylidenecamphor, and isopentyl4-methoxycinnamate. However, as the list of approved sunscreens iscurrently expanding, those of ordinary skill will recognize that theinvention is not limited to sunscreen active agents currently approvedfor human use but is readily applicable to those that may be allowed inthe future.

In one embodiment of the invention the sunscreen active agent comprisesa photoprotecting effective amount of particulates of at least oneinorganic pigment or nanopigment, non-limiting examples of which includetitanium dioxide, zinc oxide, iron oxide, zirconium oxide, cerium oxide,or mixture thereof.

The compositions of this invention can be applied to the skin as aliquid rub on, but are most commonly applied as a spray. However, thecompositions are not limited to those compositions applied to the skinprimarily as a sunscreen agent. The compositions also incorporate thoseformulations where the sunscreen active agent is an ingredient inanother topically applied composition. Some non-limiting examples arelipstick, make-up, lip-balm, eye-shadow, hair dyes and conditioners, orany application where sun protection may be deemed beneficial.

In certain embodiments of the subject invention, the compositions can bestored in containers under pressure by combination with a propellant.The compositions thus stored can be applied by opening a valve in thecontainer releasing the propellant and the composition, typically in aspray or mist. The propellant used in the composition may be anysuitable gas, or combination of gasses, that can be compressed orliquefied within a dispensing spray canister, which expand or volatilizeto vapor or gas form upon exposure to ambient temperature and pressureconditions to deliver the composition in an aerosol form. Suitablepropellants include hydrocarbons having 1 to 5 carbon atoms, includingbut not limited to methane, ethane, propane, isopropane, butane,isobutane, butene, pentane, isopentane, neopentane, pentene,hydrofluorocarbons (HFCs), chlorofluorocarbons (CFCs), nitrogen, ethersincluding dimethyl ether, and any mixtures thereof. Those of ordinaryskill in the art recognize that in a closed container such as analuminum can or glass bottle, propellants such as dimethyl ethercondense to the liquid state at ambient temperature. Thus, thecomposition in the aerosol container is liquid formulation which cancontain dissolved propellant, undissolved liquid propellant and gaseouspropellant. All of this is under pressure due to the vapor pressure ofthe propellant. In the practice of this aspect of the subject invention,the propellant can be present in an amount up to about 90 weightpercent, preferably from about 2 weight percent to about 50 weightpercent, and more preferably about 5 weight percent to about 40 weightpercent, more preferably at about 30 weight percent, based on the totalweight of the aerosol composition.

The compositions of the present invention may contain a wide range ofadditional, optional components which are referred to herein as“cosmetic components”, but which can also include components generallyknown as pharmaceutically active agents. The CTFA Cosmetic IngredientHandbook, Seventh Edition, 1997 and the Eighth Edition, 2000, which isincorporated by reference herein in its entirety, describes a widevariety of cosmetic and pharmaceutical ingredients commonly used in skincare compositions, which are suitable for use in the compositions of thepresent invention. Examples of these functional classes disclosed inthis reference include: absorbents, abrasives, anticaking agents,antifoaming agents, antioxidants, binders, biological additives,buffering agents, bulking agents, chelating agents, chemical additives,colorants, cosmetic astringents, cosmetic biocides, denaturants, drugastringents, external analgesics, film formers, fragrance components,humectants, opacifying agents, pH adjusters, plasticizers, reducingagents, skin bleaching agents, skin-conditioning agents (emollient,humectants, miscellaneous, and occlusive), skin protectants, solvents,foam boosters, hydrotropes, solubilizing agents, suspending agents(nonsurfactant), sunscreen agents, ultraviolet light absorbers, SPFboosters, waterproofing agents, and viscosity increasing agents (aqueousand nonaqueous).

The compositions of the invention may also include materials that alsoincrease the SPF of the final composition by such mechanisms as UVradiation scattering and dispersion. Such materials are referred toherein as “UV-radiation scattering agents” and comprise materials thatexhibit UV absorbing activity or exhibit no UV absorbing activity. Anexample of such UV-radiation scattering agents include polymericmaterials, such as the product known as SunSpheres™ (Rohm and Haas;Philadelphia, Pa.) which are described by their manufacturer as hollowstyrene/acrylates copolymer spheres manufactured by emulsionpolymerization. The polymer spheres are said to raise SPF values acrossthe UVA and UVB region by dispersing and/or scattering the incident UVradiation throughout the film of sunscreen present on a surface, such ashuman skin. It is understood that the spheres cause less UV radiation topenetrate into the skin by redirecting the radiation towards theUV-absorbing sunscreen actives in the sunscreen formulation, where theradiation reacts with the sunscreen active molecules and the energy isdissipated as heat. As used herein, the terms “spheres” or “scatteringagents” are not limited by chemical makeup or shape, but comprise anyagent that produces the effect of lengthening the path of incident UVradiation, increasing the statistical likelihood that the radiation willcontact a sunscreen active molecule, i.e., a UV absorbing active agent.These materials may also include UV absorbing materials that alsoexhibit scattering properties such as ZnO (examples include Z-Cote™products available from BASF), TiO₂ (examples include the Solaveiffproducts available from Uniqema (New Castle, Del., USA)), compounds suchas methylene bis-benzotriazolyl tetramethylbutylphenol, (“Tinasorb™ M”available from Ciba Specialty Chemicals, Inc. (Basel, Switzerland). UVradiation scattering agents are typically present in the formulation inamounts up to about 25% by weight. Certain example embodiments of theinvention may comprise up to about 10% by weight, preferably in rangesof about 0.5% to about 7.0% by weight, in particularly preferred rangesof 3% to about 5% by weight.

As used herein, the terms “sunless-tanning agent” or “self-tanningcompositions” refer to compositions which, when applied to human skin,impart thereto an appearance similar to that achieved by exposing theskin to natural or artificial sunlight. Examples of sunless tanningactive agents are described in U.S. Pat. Nos. 6,482,397, 6,261,541, and6,231,837. Such sunless tanning compositions typically comprise, inaddition to an artificial tanning effective amount of a self tanningagent, effective amounts of a composition coloring agent and acosmetically acceptable carrier adapted for topical application to humanskin. The self tanning agents can also include those compositionsgenerally accepted in the art for application to human skin, and which,when so applied, react therein with amino acids so as to form pigmentedproducts. Such reactions give the skin a brown appearance similar to thecolor obtained upon exposing it to sunlight for periods of timesufficient to tan the skin. Suitable self tanning agents include,without limitation, alpha-hydroxy aldehydes and ketones, glyceraldehydeand related alcohol aldehydes, various indoles, imidazoles andderivatives thereof, and various approved pigmentation agents. Presentlypreferred herein as self tanning agents are the alpha-hydroxy aldehydesand ketones. Most preferably, the self tanning agent is dihydroxyacetone(“DHA”). Other suitable self tanning agents include, without limitation,methyl glyoxal, glycerol aldehyde, erythrulose, alloxan,2,3-dihydroxysuccindialdehyde, 2,3-dimethoxysuccindialdehyde,2-amino-3-hydroxy-succindialdehyde and2-benzylamino-3-hydroxysuccindialdehyde.

An emollient is an oleaginous or oily substance which helps to smoothand soften the skin, and may also reduce its roughness, cracking orirritation. Typical suitable emollients include mineral oil having aviscosity in the range of 50 to 500 centipoise (cps), lanolin oil,coconut oil, cocoa butter, olive oil, almond oil, macadamia nut oil,aloe extracts such as aloe vera lipoquinone, synthetic jojoba oils,natural sonora jojoba oils, safflower oil, corn oil, liquid lanolin,cottonseed oil, grape seed oil, sweet almond oil, and peanut oil.Preferably, the emollient is a cocoglyceride, which is a mixture ofmono, di- and triglycerides of cocoa oil, sold under the trade name ofMyritol 331 from Henkel KGaA, or Dicaprylyl Ether available under thetrade name Cetiol OE from Henkel KGaA or a C₁₂-C₁₅ Alkyl Benzoate soldunder the trade name Finsolv TN from Finetex. One or more emollients maybe present ranging in amounts from about 1 percent to about 10 percentby weight, preferably about 5 percent by weight. Another suitableemollient is DC 200 Fluid 350, a silicone fluid, available Dow CorningCorp.

Other suitable emollients include squalane, castor oil, polybutene,sweet almond oil, avocado oil, calophyllum oil, ricin oil, vitamin Eacetate, olive oil, silicone oils such as dimethylopolysiloxane andcyclomethicone, linolenic alcohol, oleyl alcohol, the oil of cerealgerms such as the oil of wheat germ, isopropyl palmitate, octylpalmitate, isopropyl myristate, hexadecyl stearate, butyl stearate,decyl oleate, acetyl glycerides, the octanoates and benzoates of(C₁₂-C₁₅) alcohols, the octanoates and decanoates of alcohols andpolyalcohols such as those of glycol and glyceryl, ricinoleates esterssuch as isopropyl adipate, hexyl laurate and octyl dodecanoate,dicaprylyl maleate, hydrogenated vegetable oil, phenyltrimethicone,jojoba oil and aloe vera extract.

Other suitable emollients which are solids or semi-solids at ambienttemperatures may be used. Such solid or semi-solid cosmetic emollientsinclude glyceryl dilaurate, hydrogenated lanolin, hydroxylated lanolin,acetylated lanolin, petrolatum, isopropyl lanolate, butyl myristate,cetyl myristate, myristyl myristate, myristyl lactate, cetyl alcohol,isostearyl alcohol and isocetyl lanolate. One or more emollients canoptionally be included in the formulation.

A humectant is a moistening agent that promotes retention of water dueto its hygroscopic properties. Suitable humectants include glycerin,polymeric glycols such as polyethylene glycol and polypropylene glycol,mannitol and sorbitol. Preferably, the humectant is Sorbitol, 70% USP orpolyethylene glycol 400, NF. One or more humectants can optionally beincluded in the formulation in amounts from about 1 percent to about 10percent by weight, preferably about 5 percent by weight.

A dry-feel modifier is an agent which when added to an emulsion, impartsa “dry feel” to the skin when the emulsion dries. Dry feel modifiers caninclude talc, kaolin, chalk, zinc oxide, silicone fluids, inorganicsalts such as barium sulfate, surface treated silica, precipitatedsilica, fumed silica such as an Aerosil available from Degussa Inc. ofNew York, N.Y. U.S.A. Another dry feel modifier is an epichlorohydrincross-linked glyceryl starch of the type that is disclosed in U.S. Pat.No. 6,488,916.

It may be advantageous to incorporate additional thickening agents, suchas, for instance, various Carbopols available from Noveon Co.Particularly preferred are those agents which would not disrupt thelamellar structure in the formulation of the final product, such asnon-ionic thickening agents. The selection of additional thickeningagents is well within the skill of one in the art.

Additional natural or synthetic substances can also be added to thecompositions of the invention to protect from or delay its deteriorationdue to the action of oxygen in the air (oxidation). They may also reduceoxidation reactions in skin tissue. Such substances prevent oxidativedeterioration which may lead to the generation of rancidity andnonenyzymatic browning reaction products. Typical suitable substancesinclude propyl, octyl and dodecyl esters of gallic acid, butylatedhydroxyanisole (BHA, usually purchased as a mixture of ortho and metaisomers), butylated hydroxytoluene (BHT), green tea extract, uric acid,cysteine, pyruvate, nordihydroguaiaretic acid, Vitamin A, Vitamin E andVitamin C and their derivatives. One or more such substances canoptionally be included in the composition in an amount ranging fromabout 0.001 to about 5 weight percent, preferably about 0.01 to about0.5 percent.

Chelating agents are substances used to chelate or bind metallic ions,such as with a heterocylic ring structure so that the ion is held bychemical bonds from each of the participating rings. Suitable chelatingagents include ethylene diaminetetraacetic acid (EDTA), EDTA disodium,calcium disodium edetate, EDTA trisodium, albumin, transferrin,desferoxamine, desferal, desferoxamine mesylate, EDTA tetrasodium andEDTA dipotassium, or combinations of any of these.

Fragrances are aromatic substances which can impart an aestheticallypleasing aroma to the sunscreen composition. Typical fragrances includearomatic materials extracted from botanical sources (i.e., rose petals,gardenia blossoms, jasmine flowers, etc.) which can be used alone or inany combination to create essential oils. Alternatively, alcoholicextracts may be prepared for compounding fragrances. However, due to therelatively high costs of obtaining fragrances from natural substances,the modern trend is to use synthetically prepared fragrances,particularly in high-volume products. One or more fragrances canoptionally be included in the sunscreen composition in an amount rangingfrom about 0.001 to about 5 weight percent, preferably about 0.01 toabout 0.5 percent by weight.

Additional preservatives may also be used if desired and include wellknown preservative compositions such as benzyl alcohol, phenyl ethylalcohol and benzoic acid, diazolydinyl, urea, chlorphenesin,iodopropynyl and butyl carbamate, among others.

The compositions of the invention can further comprise skin protectantactive agents. Suitable examples include (with preferred weight percentranges), Allantoin (0.5 to 2 percent); Aluminum hydroxide gel (0.15 to 5percent); Calamine (1 to 25 percent); Cocoa butter (greater than 50);Cod liver oil (5 to 14 percent); Colloidal oatmeal; Dimethicone (1 to 30percent); Glycerin (20 to 45 percent); Hard fat (greater than 50);Kaolin (4 to 20 percent); Lanolin (12.5 to 50 percent); Mineral oil(greater than 50 percent); Petrolatum (greater than 30 percent); Sodiumbicarbonate; Topical starch (10 to 98 percent); White petrolatum(greater than 30 percent); Zinc acetate (0.1 to 2 percent); Zinccarbonate (0.2 to 2 percent); and Zinc oxide (1 to 25 percent).

The compositions of the invention may further include insect repellingcomponents. The most widely used insect repelling active agent forpersonal care products is N,N-Diethyl-m-toluamide, frequently called“DEET” and available in the form of a concentrate containing at leastabout 95 percent DEET. Other synthetic chemical repellents include ethylbutylacetylaminoproprionate (also known as IR 3535), dimethyl phthalate,ethyl hexanediol, indalone, di-n-propylisocinchoronate, bicycloheptene,dicarboximide and tetrahydrofuraldehyde. Certain plant-derived materialsalso have insect repellent activity, including citronella oil and othersources of citronella (including lemon grass oil), limonene, rosemaryoil and eucalyptus oil. Choice of an insect repellent for incorporationinto the sunscreen emulsion will frequently be influenced by the odor ofthe repellent. The amount of repellent agent used will depend upon thechoice of agent; DEET is useful at high concentrations, such as up toabout 15 percent or more, while some of the plant-derived substances aretypically used in much lower amounts, such as 0.1 percent or less.

Topical application of the compositions of the invention describedherein to the hair or skin of a human will provide enhanced protectionagainst deleterious effects of ultraviolet radiation (UVR). Thus, thesubject invention further provides a method for protecting human skinand/or hair against the deleterious effects of solar radiation, moreparticularly UVR, which method comprises topically applying thereto aneffective amount of the compositions as described herein. Anesthetically beneficial result of exposure of skin to UVR (i.e., lightradiation wavelengths of from 280 nm to 400 nm) is the promotion oftanning of the human epidermis. Another benefit of sun exposure comesfrom production of vitamin D within the skin. UVR is typically dividedinto UV-A (light wavelengths from 320 to 400 nm) and UV-B (wavelengthsranging from 280 to 320 nm) regions. Overexposure to UV-B irradiation isgenerally understood to lead to skin burns and erythema. In addition,overexposure to UV-A radiation may cause a loss of elasticity of theskin and the appearance of wrinkles, promoting premature skin aging.Such irradiation promotes triggering of the erythemal reaction oramplifies this reaction in certain individuals and may even be thesource of phototoxic or photoallergic reactions. It is increasinglybelieved that overexposure to UV-A may also lead to melanoma. Thus, theapplication of the compositions of the invention to the skin and/or hairof an individual will provide enhanced UVR photoprotection (UV-A and/orUV-B) of the skin and/or hair of the individual.

The sunscreen containing compositions of the invention are intended toprovide a sun protection factor (SPF) rating of at least 2, withadditional preferable embodiments having a sun protection factor of atleast 5, in another embodiment at least 10, in another embodiment atleast 15, in another embodiment at least 20, in another embodiment atleast 25, in another embodiment at least 30, in another embodiment atleast 35, in another embodiment at least 40, in another embodiment atleast 45, in another embodiment at least 50, in another embodiment atleast 55, in another embodiment at least 60, in another embodiment atleast 65, in another embodiment at least 70, in another embodiment atleast 75, in another embodiment at least 80, in another embodiment atleast 85, in another embodiment at least 90, in another embodiment atleast 95, and in another embodiment at least 100. The sunscreencontaining compositions of the invention are also intended to provideU.S. FDA UV-A “star ratings” of at least one star, at least two stars,at least three stars and up to four stars. As demonstrated herein, byneutralizing the acid groups of the film forming polymer, a boost in SPFcan be obtained while maintaining the amount of sunscreen active agentload in the composition. Thus, in an example embodiment of theinvention, for two compositions containing equal amounts of sunscreenactive agents, the SPF for the composition containing the partially orfully neutralized film forming agent may be greater than 125 percent ofthe composition containing un-neutralized film forming agents. Inalternative example embodiments, the SPF for the composition containingthe partially or fully neutralized film forming agent may be greaterthan 150 percent of the un-neutralized formulation, greater than 200percent of the un-neutralized formulation, or greater than 300 percentof the un-neutralized formulation. Alternatively stated, an SPF greaterthan 125 percent of un-neutralized SPF is equivalent to saying the SPFfor a composition containing the partially or fully neutralized polymeris greater than 1.25 times that which would be achieved using anun-neutralized formulation.

The invention will be further described by means of the followingexamples, which are not intended to limit the invention, as defined bythe appended claims, in any manner.

Example 1 Sunscreen Composition

A sunscreen composition was prepared containing amine neutralizingagents and film forming polymer as follows. To a 250 ml beaker was added3.0 g Avobenzone, 5.0 g Octisalate, 6.0 g Oxybenzone, 15.0 g Homosalate,and 1.0 g of Glycerine to a stirred solution containing 0.51 g ofDimethylstearylamine and 3.0 g of Dermacryl 79 (an acrylate copolymercontaining 14% acrylic acid, available from National Starch and ChemicalCo. Bridgewater, N.J.) in 66.49 g of Ethanol. The composition wasstirred until all components are dissolved. Similar compositions can beheated slightly to aid in dissolution.

Example 2 Evaluation of Effect of Neutralization on SPF of SunscreenFormulations

Sunscreen compositions were prepared as described above with varyinglevels and types of amine neutralizing agents. All compositions in thisexample contained Avobenzone (3.0 g), Octyl Salicylate (5.0 g),Oxybenzone (6.0 g), Homosalate (15.0 g), glycerin (1.0 g) and Dermacryl79 (3.0 g) plus ethanol to bring the weight to 100 g.

All SPF measurements were conducted using poly(methyl methacrylate)(PMMA) plates (Schonberg GMBH & Co KG., 22457 Hamburg-Schnelsen,Germany) as the substrate to which the sunscreen formulas were applied.Test formulations were applied to the substrates at 1 mg/cm² and allowedto dry for 20 minutes. A PMMA plate treated with glycerin at 1 mg/cm²served as a reference and blank. The in vitro SPF of each formula wasdetermined using an Optometrics SPF 290S Analzyer (Optometrics LLC,Ayer, Mass.; USA) equipped with a computer-controlled X-Y sampling stageand operated according to the manufacturer's instructions. A total of 12in vitro SPF values were obtained for each formula using a different,non-overlapping position on each mounted substrate. All the SPF valuesreported are the average of 12 values measured for each formulation.

The results are shown in Table 2.

TABLE 2 SPF as a function of neutralization. Dimethyl Percent 25% EtOH/Triethanol Stearyl neutralization SPF KOH amine amine of carboxylic in-Sample (grains) (grams) (grams) acid groups vitro 1 0 0 0 0 31 2 0.38 1027 3 0.95 25 33 4 1.90 50 28 5 0.10 10 37 6 0.25 25 14 7 0.50 50 21 80.20 10 51 9 0.51 25 56 10 1.01 50 141The results in Table 2 show the significant improvement in measured invitro SPF with as little as 10 percent neutralization of the filmforming polymer (sample 8) and that even higher levels of protectionsare possible with higher neutralization (sample 9 and 10).

Example 3 Various Amines Used for SPF Boost

Sunscreens were prepared as described in Example 2 to which theindicated amines (Table 3) were added in an amount to neutralize 25percent of the carboxylic acid groups on the Dermacryl 79. Testformulations were applied to the PMMA substrate at 2 mg/cm² and analyzedfor SPF performance. The results are shown in Table 3:

TABLE 3 Sample # Amine SPF 11 Propylamine 45 12 Butylamine 53 13Hexylamine 82 14 Octylamine 102 15 Decylamine 93 16 Dodecylamine 76 17Diethylamine 63 18 Dihexylamine 81 19 Triethylamine 54 20 Tributylamine25 21 Dimethylaminopropylcocamide 69 22 Cocamine 83 23 Dimethylcocamine52 24 Dimethylstearylamine 65 25 Soyamine 64 26 Dimethylsoyamine 63 27Dimethylerucylamine 83 28 Dimethylbehenylamine 62 29 PEG-15 Cocamine 5630 PEG-15 Soyamine 63 31 PEG-2 Behenylamine 71 32 Jeffamine M-1000 57 33Jeffamine M-2070 34 34 Control no neutralizer 39Sample 34 represents the control with no neutralization. Theseexperiments show that, although compositions containing certain of theamines do not demonstrate a substantial boost in SPF, compositionscontaining examples of a wide variety of amines provide a large boost inSPF over the control.

Example 4 In Vivo SPF and Very Water Resistant Assays

Three sunscreen formulations were prepared and tested for sunscreenefficacy in a human SPF assay and Very Water Resistant Assay (FDA FinalMonograph Protocol 7.22). The three formulations are Samples 1, 9, and10 from Table 2 above. All three formulations were Ethanol basedcompositions containing, 3% Avobenzone, 5% Octyl Salicylate, 6%Oxybenzone, 15% Homosalate, 1.0% glycerin, 3% Dermacryl 79 (allpercentages by weight of final formulation). The three formulationsdiffered with respect to the percent neutralization of carboxylic acidgroups of the film forming agent. Sample 1 had 0% neutralization, Sample9 had 25% neutralization and Sample 10 had 50% neutralization. The amineneutralizing agent used for Samples 9 and 10 was dimethylstearylamine,which was added in an amount to achieve the desired neutralizationlevel.

The SPF testing on each sample was conducted (according to Protocol7.22) by first measuring the pre-immersion (static) average SPF,carrying out the immersion procedure, and then a second measurement postimmersion to calculate very water resistant average SPF. Five subjectswere tested for each sample. Results are shown in Table 4.

TABLE 4 Sample Avg SPF pre-immersion Avg SPF post-immersion 1 31.8 29.29 56.5 55.8 10 78.3 78.3* *N = 4 for Sample 10 post-immersion. One ofthe five subjects exhibited erythema in all sub-sites to which the testcomposition was applied after water immersion. According to standardprocedures, this subject was not used to calculate the average SPF valuepost immersion for Sample 10.

The data in Table 4 prove that the compositions of the invention providea substantially increased in vivo SPF based on the presence of theamine-neutralized film forming agent and the formulations withstood VeryWater Resistant Assay testing. Sample 9 (comprising 25% neutralization)showed an SPF of 178% (pre-immersion) and 191% (post-immersion) of theSPF of Sample 1. Sample 10 (comprising 50% neutralization) showed an SPFof 246% (pre-immersion) and an SPF of 268% (post immersion) of the SPFof Sample 1. The data demonstrate the compositions of the invention arevery water resistant sunscreen compositions based on the negligibledifferences between the pre- and post-immersion SPF values.

Example 5 Example Formulations

Table 5 describes example formulations comprising water content of 30%and percent neutralization of film forming agent (e.g. Dermacryl 79) of25%.

TABLE 5 Example Formulas Ex 35 Ex 36 Ex 37 Ex 38 Ex 39 Ingredients %(w/w) % (w/w) % (w/w) % (w/w) % (w/w) Part A Dermacryl 79 3.00 3.00 5.003.00 5.00 Dimethylsoyamine 11.70 6.72 6.07 4.92 8.79 Ethanol 41.30 51.2840.93 51.08 40.21 Part B water 30.00 30.00 30.00 30.00 30.00 glycerin3.00 3.00 3.00 3.00 3.00 Part C Sulisobenzone 5.00 4.00 3.00 0.00 3.00Enzulizole 2.00 2.00 2.00 2.00 2.00 Disodium Phenyl 2.00 0.00 0.00 0.003.00 Dibenzimidazole Tetrasulfonic Acid Ecamsule 2.00 0.00 0.00 2.000.00 Part D Tinosorb M* 0.00 0.00 10.00 0.00 5.00 Zinc Oxide 0.00 0.000.00 2.00 0.00 Titanium Dioxide 0.00 0.00 0.00 2.00 0.00 Total 100.00100.00 100.00 100.00 100.00 (*Tinosorb M is trade name for methylenebis-benzotriazolyl tetramethylbutylphenol, an organic particulatesunscreen active)The Part A components are combined by adding Dermacryl 79 to ethanol,followed by addition of Dimethylsoyamine and mixing. The Part Bcomponents water and glycerin are then to the mixture of Part A. Thesunscreen actives of Part C are then added and mixed until dissolved.The particulate sunscreen actives of Part D (if included) are added tothe mixture until dispersed. Although the formulations described abovedemonstrate use of hydrophilic sunscreen actives, formulationscomprising hydrophobic sunscreen actives can be similarly prepared bythe ordinary practitioner using methods to solubilize the actives in theformulations.

Although certain presently preferred embodiments of the invention havebeen described herein, it will be apparent to those skilled in the artto which the invention pertains that variations and modifications of thedescribed embodiments may be made without departing from the spirit andscope of the invention.

We claim:
 1. A film forming composition comprising at least one film forming polymer containing a plurality of acid groups, wherein at least a portion of the acid groups have been neutralized with a cosmetically acceptable neutralizing agent, wherein the film forming composition exhibits a boost to SPF in sunscreen compositions by 125% compared to the SPF of sunscreen compositions that do not include the film forming composition, wherein the cosmetically acceptable amine based neutralizing agent is selected from an agent having the structure:

wherein R₈ is C₂ to about C₃₆ straight chain, branched or cyclic alkyl, alkenyl, alkynyl, aryl, aralkyl, aralkenyl, or aralkynyl group, and R9 is selected from H or CH₃, or C₂ to C₃₆ straight chain, branched or cyclic alkyl, alkenyl, alkynyl, aryl, aralkyl, aralkenyl, or aralkynyl group, and wherein x and y are independently 1 to 100 and wherein said straight chain, branched or cyclic alkyl, alkenyl, alkynyl, aryl, aralkyl, aralkenyl, or aralkynyl groups can optionally contain one or more heteroatoms;

wherein R₁₀ R₁₁, and R₁₂ are independently selected from H, CH₃ or C₂ to about C₃₆ straight chain, branched or cyclic alkyl, alkenyl, alkynyl, aryl, aralkyl, aralkenyl, or aralkynyl group, and wherein n is 1 to 100 and wherein said straight chain, branched or cyclic alkyl, alkenyl, alkynyl, aryl, aralkyl, aralkenyl, or aralkynyl groups can optionally contain one or more heteroatoms;

wherein R₆ is H or CH₃ and x and y are independently from about 1 to about 100;

wherein x is from about 1 to about 100;

wherein x, y and z are independently from about 1 to about 100; and

wherein R₇ is H or C₂H₅ and n, x, y and z are independently from about 1 to about
 100. 2. The composition of claim 1, wherein the amine-based neutralizing agent is selected from an agent having the structure:

wherein R₈ is C₂ to about C₃₆ straight chain, branched or cyclic alkyl, alkenyl, alkynyl, aryl, aralkyl, aralkenyl, or aralkynyl group, and R₉ is selected from H or CH₃, or C₂ to C₃₆ straight chain, branched or cyclic alkyl, alkenyl, alkynyl, aryl, aralkyl, aralkenyl, or aralkynyl group, and wherein x and y are independently 1 to 100 and wherein said straight chain, branched or cyclic alkyl, alkenyl, alkynyl, aryl, aralkyl, aralkenyl, or aralkynyl groups can optionally contain one or more heteroatoms; or

wherein R₁₀ R₁₁, and R₁₂ are independently selected from H, CH₃ or C₂ to about C₃₆ straight chain, branched or cyclic alkyl, alkenyl, alkynyl, aryl, aralkyl, aralkenyl, or aralkynyl group, and wherein n is 1 to 100 and wherein said straight chain, branched or cyclic alkyl, alkenyl, alkynyl, aryl, aralkyl, aralkenyl, or aralkynyl groups can optionally contain one or more heteroatoms.
 3. The composition of claim 1, wherein the amine-based neutralizing agent is selected from an agent having the structure:

wherein R₈ is C₂ to about C₃₆ straight chain, branched or cyclic alkyl, alkenyl, alkynyl, aryl, aralkyl, aralkenyl, or aralkynyl group, and R₉ is selected from H or CH₃, or C₂ to C₃₆ straight chain, branched or cyclic alkyl, alkenyl, alkynyl, aryl, aralkyl, aralkenyl, or aralkynyl group, and wherein x and y are independently 1 to 100 and wherein said straight chain, branched or cyclic alkyl, alkenyl, alkynyl, aryl, aralkyl, aralkenyl, or aralkynyl group can optionally contain one or more heteroatoms.
 4. The composition of claim 1, wherein the film forming polymer comprises two or more distinct monomer units, wherein at least one of said monomers comprises a carboxylic acid moiety.
 5. The composition of claim 1, wherein said film forming polymer comprises a plurality of distinct monomers wherein at least one of said monomers comprises from about 5 to about 95 percent of the total monomer content.
 6. The composition of claim 1, wherein said film forming polymer comprises a plurality of distinct monomers wherein at least one of said monomers comprises from about 5 to about 50 percent of the total monomer content.
 7. The composition of claim 1, wherein from about 5 to about 100 percent of the plurality of acid groups of the film forming polymer are neutralized by said amine-based neutralizing agent.
 8. The composition of claim 1, wherein from about 5 to about 50 percent of the plurality of acid groups of the film forming polymer are neutralized by said amine-based neutralizing agent.
 9. The composition of claim 1, wherein said acid groups on the film forming polymer are chosen from the group consisting of carboxylic acids, sulfonic acids, phosphoric acids, and combinations thereof.
 10. The composition of claim 1, wherein said at least one film forming polymer is chosen from polyacrylic acid, polycrotonic acid, polymethacrylic acid, polymaleic acid, polyitaconic acid, octylacrylamide/acrylates/butylaminoethyl methacrylate copolymer, acrylates/octylacrylamide copolymer, acrylates copolymer, octylacrylamide/butylaminoethyl methacrylate copolymer, VA/crotonates/vinyl neodecanoate copolymer, VA/Crotonates copolymer, sodium polystyrene sulfonate, polyurethane-14 (and) AMP-Acrylates copolymer, acrylates/octylacrylamide copolymer, acrylates/steareth-20 itaconate, copolymer, acrylates/ceteth-20 itaconate copolymer, PVM/MA half ethyl ester copolymer, butylated PVP, PVP/hexadecene copolymer, PVP/eicosene copolymer, tricontanyl PVP, butyl ester of PVM/MA copolymer, PVM/MA copolymer, ethyl ester of PVM/MA copolymer, butyl ester of PVM/MA copolymer, vinyl caprolactam/PVP/dimethylaminoethyl methacrylate copolymer, polyquaternium-11, polyquaternium-28, Polyimide-1, PVP/Vinylcaprolactam/DMAPA Acrylates Copolymer, Isobutylene/Ethylmaleimide/Hydroxyethylmaleimide Copolymer, Acrylates/C1-2 Succinates/Hydroxyacrylates Copolymer, PVP/DMAPA Acrylates Copolymer, VP/Acrylates/Lauryl Methacrylate Copolymer, Polyquaternium-55, PVP/Dimethylaminoethylmethacrylate Copolymer, VinylcaprolactamNP/Dimethylaminoethyl Methacrylate Copolymer, VA/Butyl Maleate/Isobornyl Acrylate Copolymer, acrylic acid/ethyl acrylate/t-butyl acrylamide, t-butyl acrylate/ethyl acrylate/methacrylic acid, ethyl acrylate/t-butyl acrylate/methacrylic acid, polyquaternium-16, polyquaternium-16, PVP, PVPNA copolymer, PVPNA copolymer, Polyurethane-1, VP/MethacrylamideNinyl Imidazole Copolymer, Acrylates Copolymer, Acrylates/Acrylamide Copolymer, Polyvinylcaprolactam, Dimethicone/Acrylates Copolymer; Amerchol, acrylic acid/methacrylic acid/acrylates/methacrylates, acrylic acid/methacrylic acid/acrylates/methacrylates/hydroxy ester acrylates; methacryloyl ethyl betaine/acrylates copolymer, Acrylates/Hydroxyesters Acrylates Copolymer, Ethylenecarboxyamide/AMPSA/Methacrylates Copolymer, methacrylic acid/sodium acrylamidomethyl propane sulfonate copolymer, AMP-Acrylates/Allyl Methacrylate Copolymer, Polyacrylates-X, Acrylates/C10-30 Alkyl Acrylates Copolymer, Acrylates Copolymer, Polyurethane-2, Polyurethane-4, PPG-17/IPDI/DMPA Copolymer; polyethylene glycol; water-soluble acrylics; water-soluble polyesters; polyacrylamides; polyamines; polyquaternary amines; styrene maleic anhydride (SMA) resin; or mixtures or combinations thereof.
 11. The composition of claim 1 further comprising a volatile solvent.
 12. The composition of claim 11 wherein the solvent is selected from the group consisting of ethanol, isopropanol, methanol and acetone.
 13. A method for producing a film-forming composition comprising neutralizing at least a portion of the acid groups of an acid group-containing film forming polymer with a cosmetically acceptable amine-based neutralizing agent, and wherein the film forming composition of the neutralized film-forming polymer provides a boost to SPF in sunscreen compositions by 125% compared to the SPF of sunscreen compositions that do not include the film forming composition.
 14. The method of claim 13, wherein at least 5% of the acid groups of the film forming polymer are neutralized by the amine-based neutralization agent.
 15. The method of claim 13, wherein at least 10% of the acid groups of the film forming polymer are neutralized by the amine-based neutralization agent.
 16. The method of claim 13, wherein at least 25% of the acid groups of the film forming polymer are neutralized by the amine-based neutralization agent.
 17. The method of claim 13, wherein at least 50% of the acid groups of the film forming polymer are neutralized by the amine-based neutralization agent.
 18. The method of claim 13, wherein the film forming composition boosts SPF in sunscreen compositions by 150% compared to the SPF of sunscreen compositions that do not include the film forming composition.
 19. The method of claim 13, wherein the film forming composition boosts SPF in sunscreen compositions by 200% compared to the SPF of sunscreen compositions that do not include the film forming composition.
 20. The method of claim 13, wherein said amine neutralizing agent is alkylamine, alkenylamine, dialkylamine, dialkenylamine, dimethyl alkylamine, methyl dialkylamine, triakylamine, dimethyl alkenylamine, methyl dialkenylamine, trialkenylamine, or a combination or mixture thereof.
 21. The method of claim 13, wherein said acid groups on the film forming polymer comprise carboxylic acid groups, sulfonic acid groups, phosphoric acid groups, or a combination thereof. 